PNNL

Abstract

Abstract: An ab initio theoretical study shows that a previously neglected intra-atomic many-body effect has important consequences for the X-ray photoelectron spectra (XPS) of transition metal atoms and cations. For the Mn 3s XPS, inclusion of this effect correctly yields the multiplet splitting, properly describes the absolute binding energy, and predicts new satellite structure. It is not necessary to invoke an artificial scaling of the two electron integrals to improve agreement with experiment. This intra-atomic effect is expected to be of general importance and a proper interpretation of the XPS spectra requires that it be taken into account.